Abstract
The polymerization of tert-butyl acrylate (tBA) was performed with triethylaluminum-(−)-sparteine, triethylaluminum–tertiary phosphine, triethylaluminum–n-BuLi and bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum–t-BuLi complexes in toluene. The poly(tBA)s obtained with these initiators were rich in syndiotactic diad as observed by 1H NMR analysis. On the basis of the triad and tetrad stereochemical information of the poly(tBA)s obtained using triethylaluminum-(−)-sparteine and triethylaluminum–n-BuLi, the polymerization reactions were found to obey Bernoullian statistics. Glass transition temperatures of the poly(tBA)s were measured by differential scanning calorimetry (DSC). A syndiotactic poly(tBA) (racemo (r) diad content: 65%) and an isotactic one (r=19%) exhibited higher glass transition temperature (50 and 43°C, respectively) than an atactic one (r=50%,Tg=21°C).
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